EP0363866A2 - Triesters d'acides carboxyliques supérieurs d'adamantetriol et huiles lubrifiantes les contenant - Google Patents

Triesters d'acides carboxyliques supérieurs d'adamantetriol et huiles lubrifiantes les contenant Download PDF

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EP0363866A2
EP0363866A2 EP89118697A EP89118697A EP0363866A2 EP 0363866 A2 EP0363866 A2 EP 0363866A2 EP 89118697 A EP89118697 A EP 89118697A EP 89118697 A EP89118697 A EP 89118697A EP 0363866 A2 EP0363866 A2 EP 0363866A2
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Prior art keywords
adamantane
triol
reaction
carboxylic acid
higher carboxylic
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German (de)
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EP0363866A3 (fr
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Kosaku Idemitsu Kosan Compagny Limited Honna
Hiromichi Idemitsu Kosan Compagny Limited Seiki
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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Priority claimed from JP25499788A external-priority patent/JPH02104553A/ja
Priority claimed from JP1017253A external-priority patent/JP2678784B2/ja
Application filed by Idemitsu Kosan Co Ltd filed Critical Idemitsu Kosan Co Ltd
Publication of EP0363866A2 publication Critical patent/EP0363866A2/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
    • C07C2603/74—Adamantanes

Definitions

  • the present invention relates to a higher carboxylic acid triester of adamantane triol as a novel compound and a syn­thetic lubricating oil containing the same. More particularly, the present invention relates to a higher carboxylic acid tri­ester of adamantane triol which is a novel compound useful as a constituent of high-performance synthetic lubricating oils excellent in both of the low-temperature characteristics and high-temperature characteristics as well as to a high-performance synthetic lubricating oil containing the compound which can be used quite satisfactorily as an engine oil, gear oil, hydraulic working fluid, grease, vacuum pump oil, bearing-impregnating oil, gas turbine oil and the like.
  • Synthetic lubricating oils known in the prior art include polyolefins such as oligomers of ⁇ -olefin, polyisobutylene and the like, organic ester compounds such as diesters, e.g., di(2-ethylhexyl) sebacate, alkyl esters of pentaerithritol and the like, polyphenyl ethers such as m-bis(m-phenoxyphenoxy) benzene and the like, phosphate esters such as tricresyl phos­phate and the like, polyalkylene glycols such as polypropylene glycol and the like, silicone fluids, perfluoroalkyl ethers and so on.
  • polyolefins such as oligomers of ⁇ -olefin, polyisobutylene and the like
  • organic ester compounds such as diesters, e.g., di(2-ethylhexyl) sebacate, alkyl
  • Japanese Patent Publication No. 46-22465 discloses a diester of adamantane-­1,3-diol represented by the general formula in which R4 is a hydrogen atom or an alkyl or cycloalkyl group having 1 to 20 carbon atoms and R5 and R6 are each an alkyl or cycloalkyl group having 1 to 20 carbon atoms.
  • ester compounds of adamantane when used as a con­stituent of a synthetic lubricating oil, have a defect in respect of the viscosity-temperature characteristics although excellent heat resistance can be obtained therewith.
  • a diester of adamantane-1,3-diol of which the groups denoted by R4 and R5 in the above given general formula (I) are each a methyl group and the group denoted by R6 is an octyl group, has a kinematic viscosity of 7.1 centistokes at 100°C, viscosity index of 95 and pour point of -50°C or below so that this diester compound could be used as a high-performance synthetic lubricating oil if each of the viscosity at high temperatures and the viscosity index would have a still higher value.
  • the present invention accordingly has an object to provide a novel derivative of adamantane useful as a constituent of a high-performance synthetic lubricating oil which is excellent in both of the low temperature characteristics and high tempera­ture characteristics and to provide a synthetic lubricating oil containing the compound.
  • the novel adamantane derivative provided by the present invention is a higher carboxylic acid triester of adamantane triol represented by the general formula in which Z is a hydrogen atom or a hydroxyl group and R1, R2 and R3 are each, independently from the others, an alkyl or cycloalkyl group having 4 to 30 carbon atoms.
  • Figures 1, 2 and 3 are each a diagram of a 13C NMR spectrum, 1H NMR spectrum and infrared absorption spectrum, respectively, of a higher carboxylic triester of adamantane triol according to the present invention.
  • the higher carboxylic acid triester of adamantane triol represented by the above given general formula (II) is a novel compound not known in the prior art nor described in any literatures.
  • Each of the groups denoted by R1, R2 and R3 in the above given general formula (II) is, independently from the others, an alkyl or cycloalkyl group having 4 to 30 carbon atoms. Although these three groups can be different from each other, it is preferable that all of these groups are of the same kind in view of the higher efficiency in the synthetic preparation of the compound.
  • the symbol Z in the general formula (II) denotes a hydrogen atom or a hydroxyl group.
  • a higher carboxylic acid triester of adamantane-1,3,5-­triol or, namely, a compound of the general formula (II) of which Z is a hydrogen atom can be prepared by the esterifica­tion of adamantane-1,3,5-triol with a higher carboxylic acid or a reactive derivative thereof corresponding to the groups denoted by R1, R2 and R3.
  • a higher carboxy­lic acid triester of 7-hydroxy adamantane-1,3,5-triol or, namely, a compound of the general formula (II) of which Z is a hydroxyl group can be prepared by the esterification of adamantane-­1,3,5,7-tetraol with a higher carboxylic acid or a reactive derivative thereof corresponding to R1, R2 and R3.
  • 1,3,5-triol and 1,3,5,7-tetraol of adamantane can be prepared, according to the reaction scheme A shown below, by oxidizing adamantane (III) into an adamantane diol (IV) which is further oxidized to give adamantane-1,3,5-­triol (V) or adamantane-1,3,5,7-tetraol (VI).
  • the method for the oxidation of adamantane (III) into the adamantane diol (IV) is not particularly limitative and any of known oxidation methods can be applied thereto.
  • Applicable methods include air oxidation in the presence of a metal salt-based oxidation catalyst and oxidation with chromium trioxide in acetic acid as a solvent, of which the latter method is preferred.
  • adamantane is added to and suspended in acetic acid to give a slurry to which an aqueous solution of chromium trioxide is added dropwise to effect the oxidation reaction.
  • the acetic acid is used in such an amount that the molar ratio of acetic acid to adamantane is preferably in the range from 3 to 7.
  • the chromium trioxide is used in such an amount that the molar ratio thereof to the adamantane is preferably in the range from 4 to 8.
  • the concentration of chromium trioxide in the aqueous solution should be as high as possible so that the aqueous solution is usually a saturated solution of chromium trioxide.
  • the oxidation reaction is performed usually at a tempera­ture in the range from 80 to 120°C.
  • a tempera­ture in the range from 80 to 120°C.
  • the reaction tempera­ture is too low, the reaction velocity would be impractically low while, when the reaction temperature is too high, undesir­able side reactions may take place predominantly.
  • the length of time taken for completion of the oxidation reaction naturally depends on various conditions such as the reaction temperature, amount of chromium trioxide used and the like but the reaction is complete usually within 1 to 20 hours.
  • the reaction mixture After completion of the oxidation reaction, the reaction mixture is usually freed from acetic acid as the solvent by distillation under reduced pressure, neutralized with an alkali and then subjected to extraction of the reaction product by using a suitable organic solvent to give an extract from which the reaction product is isolated by a known method in the form of crude adamantane diol (IV).
  • the crude adamantane diol obtained in the above described manner can be used usually as such without further purification in the second step oxidation reaction, in which the reaction conditions are about the same as in the above described first step oxidation reaction by using chromium trioxide as the oxid­izing agent followed by the post-treatment of the reaction product.
  • the proportion of the yields of adamantane-1,3,5-­triol (V) and adamantane-1,3,5-,7-tetraol (VI) in the resultant reaction mixture can be controlled by adequately selecting the conditions in the oxidation reaction of the diol with chromium trioxide.
  • the crude reaction product after the above mentioned post-treatment can be esterified as such although it is optional that the crude reaction product is purified by a suitable means to isolate the triol and tetraol in a pure form to be used as the starting material of the esterification reaction.
  • the adamantane diol (IV) can be prepared by a method other than the direct oxidation of adamantane with chromium trioxide. For example, adamantane is first brominated to give a dibromo adamantane which is reacted with an aqueous solution of silver sulfate and then oxidized with chromium trioxide to give the diol.
  • adamantane-­1,3,5-triol and adamantane-1,3,5,7-tetraol can be synthesized via several other synthetic routes, for example, shown by the reaction schemes B and C described below.
  • adamantane (III) is first brominated with bromine in the presence of aluminum bromide as a catalyst to give 1,3,5-tribromo adamantane (VII) and 1,3,5,7-tetrabromo adamantane (VIII) which are then reacted with an aqueous solution of silver sulfate to give adamantane-1,3,5-triol (V) and adamantane-1,3,5,7-tetraol (VI).
  • adamantane (III) is first subjected to autoxidation with air or oxygen to give an adamantane compound (IX) having hydroxyl groups and oxo groups and then the oxo groups are reduced with hydrogen to give adamantane-1,3,5-triol (V).
  • the adamantane triol can be obtained by the hydrolysis of a tribromo adamantane compound in the presence of a tertiary amine compound.
  • the tribromo admantane as the starting material of this method includes 1,3,5-tribromo adamantanes, 1,3,6-tribromo adamantanes, represented by the following general formulas (X) and (XI), respectively, and the like:
  • the symbol R7 denotes a hydrogen atom or a substituent group not inhibitive against the reaction, which is exemplified by lower alkyl groups such as methyl, ethyl, propyl and butyl groups.
  • These tribromo adamantane compounds can easily be obtained, for example, by the bromination of adamantane in the presence of aluminum bromide as a catalyst.
  • the tribromo adamantane obtained in this method usually contains dibromoadamantane compounds and tetrabromo adamantane compounds as impurities.
  • the content of these impurities in the adamantane triol should not exceed 5% by weight or, desirably, 2% by weight.
  • the tertiary amine compound used in the above mentioned hydrolysis reaction includes trimethyl amine, triethyl amine, 1,8-diazabiscyclo[5.4.0]undecene-7 (DBU), pyridine compounds and the like, of which pyridine compounds are particularly preferred. These tertiary amine compounds can be used either singly or as a combination of two kinds or more according to need.
  • pyridine compounds include pyridine and substituted pyridines represented by the general formula in which R8 is a substituent group not inhibitive against the reaction such as lower alkyl groups, e.g., methyl and ethyl groups, di(lower alkyl)-substituted amino groups, e.g., di­methyl amino and diethyl amino groups, and the like and the subscript n is zero or an integer not exceeding 5 while, when n is 2 or larger, each of the groups denoted by R8 can be independent from the others.
  • R8 is a substituent group not inhibitive against the reaction
  • R8 is a substituent group not inhibitive against the reaction
  • R8 is a substituent group not inhibitive against the reaction
  • R8 is a substituent group not inhibitive against the reaction
  • R8 is a substituent group not inhibitive against the reaction
  • R8 is a substituent group not inhibitive against the reaction
  • R8 is a substituent group not inhibitive against the reaction
  • the hydrolysis reaction of the tribromo adamantane is carried out in the presence of one kind or more of these tertiary amine compounds with addition of water, the amount of which is usually in the range from 10 to 200 moles or, preferably from 20 to 150 moles per mole of the tribromo adamantane.
  • water usually in the range from 10 to 200 moles or, preferably from 20 to 150 moles per mole of the tribromo adamantane.
  • the amount of water is too small, the adamantane triol as the reaction product cannot be completely dissolved in the reaction mixture to form a slurry-like mix­ture so that smooth proceeding of the reaction is somewhat disturbed.
  • the reaction velocity may be disadvantageously decreased due to the decrease in the concentration of the tribromo adamantane as the starting material in the reaction mixture.
  • the amount of the tertiary amine com­pound added to the reaction mixture is usually in the range from 5 to 60 moles or, preferably, from 10 to 50 moles per mole of the tribromo adamantine compound.
  • the amount of the tertiary amine compound is too small, the tribromo adamantane compound cannot be completely dissolved in the reaction mixture to form an inhomogeneous reaction mixture so that smooth proceeding of the reaction is somewhat disturbed.
  • the reaction velocity may be disadvan­tageously decreased in addition to the economical disadvantage that a large amount of the tertiary amine compound must be recovered from the reaction mixture and recycled.
  • the hydrolysis reaction is carried out at a temperature, usually, in the range from 150 to 280°C or, preferably, in the range from 170 to 250°C.
  • a temperature usually, in the range from 150 to 280°C or, preferably, in the range from 170 to 250°C.
  • the pressure in the reaction is not particularly limitative and the reaction is usually performed under a spontaneously produced pressure at the temperature.
  • the time taken for completion of the reaction naturally depends on various conditions of the reaction such as amount of water added to the reaction mixture, kind and amount of the tertiary amine compound, reaction temperature and so on but the reaction is usually complete within 0.5 to 20 hours.
  • the reaction can be conducted in a batch process, semi-­continuous process or continuous process.
  • the above described hydrolysis reaction to form the adaman­tane triol compound is usually accompanied by the formation of various by-products including dehydroadamantane diols, di­bromo adamantanols, monobromo adamantane diols and the like.
  • dehydroadamantane diols can readily be converted into corresponding adamantane triol compounds when they are heated in an acidic aqueous solution.
  • the amounts of the dibromo adamantanols and monobromo adamantane diols as the by-products can be decreased by appropriately selecting the reaction conditions since these compounds are intermediate products formed in an increased amount when the reaction is performed under mild reaction conditions.
  • reaction mixture after completion of the above described hydrolysis reaction is then subjected to a post-­treatment preferably in the following manner.
  • the reaction mixture after completion of the hydrolysis reaction is admixed with an alkali metal hydroxide such as sodium hydroxide and potassium hydroxide with an object that, since a part of the tertiary amine compound in the reaction mixture is contained in the mixture in the form of a pyridinium salt with the hydrogen bromide produced by the reaction, the pyridinium salt of the amine compound is decomposed to isolate the amine compound in the free form. Thereafter, the reaction mixture is distilled to remove the thus isolated tertiary amine compound and water.
  • an alkali metal hydroxide such as sodium hydroxide and potassium hydroxide
  • the residue of distillation is then admixed with diluted sulfuric acid of a concentration of about 3 to 10% by weight and heated at a temperature, usually, in the range from 50 to 100°C to effect hydration of the de­hydroadamantane diols as the by-products followed by neutraliza­tion with an alkali.
  • diluted sulfuric acid of a concentration of about 3 to 10% by weight and heated at a temperature, usually, in the range from 50 to 100°C to effect hydration of the de­hydroadamantane diols as the by-products followed by neutraliza­tion with an alkali.
  • the unreacted tribromo adamantane com­pounds are removed from the mixture by a suitable means such as filtration.
  • the filtrate after removal of the unreacted tribromo adamantanes is distilled to remove water and the residue after distillation is subjected to extraction with an organic solvent such as lower alcohols to give an extract from which the organic solvent is removed by distillation so that the desired product of the adamantane triols can be obtained as a residue in a crystalline form.
  • the unreacted tribromo adamantanes recovered above can be recycled as such to the step of hydrolysis.
  • the recycled amount is usually in the range from 2 to 30% by weight based on the overall amount of the charged starting material.
  • the adamantane triol compounds can be used satisfactorily not only as the intermediate material for the preparation of the triester compounds useful as a high-performance synthetic lubricating oil but also as an intermediate for the synthetic preparation of various kinds of industrially important organic chemicals.
  • the higher carboxylic acid used in the esterification of the adamantane triols and tetraols is represented by the general formula R-CO-OH, in which R is an alkyl group or cycloalkyl group having 4 to 30 carbon atoms.
  • R is an alkyl group or cycloalkyl group having 4 to 30 carbon atoms.
  • Particular examples of the higher carboxylic acid include caproic acid, isovaleric acid, n-heptanoic acid, caprylic acid, pelargonic acid, capric acid, n-undecylic acid, lauric acid, myristic acid, plamitic acid, stearic acid, eico­sanoic acid, behenic acid, cyclohexane carboxylic acid, deca­hydronaphthalene carboxylic acid and the like.
  • the reactive derivatives of the above mentioned higher carboxylic acid in­clude lower alkyl esters, acid chlorides, acid anhydrides and the like
  • the esterification reaction is performed usually by using from 3 to 6 moles of the above mentioned higher carboxylic acid or a reactive derivative thereof per mole of the adaman­tane triol compound, e.g., adamantane-1,3,5-triol, or adaman­tane-1,3,5,7-tetraol.
  • the amount of the higher carboxylic acid or a reactive derivative thereof is too small, the relative amount of the monoester and diester as the undesirable by-products is naturally increased while no particular ad­ditional advantages can be obtained by increasing the amount of the higher carboxylic acid or a reactive derivative thereof over the above mentioned upper limit.
  • the esterification re­action is carried out usually at a temperature in the range from 50 to 150°C.
  • the reaction temperature is too low, the reaction velocity is impractically low while an exces­sively high reaction temperature may result in predominance of undesirable side reactions.
  • reaction mixture after completion of the esterifica­tion reaction is processed according to a conventional procedure to isolate higher carboxylic acid triesters of adamantane triol compounds of the present invention represented by the general formula in which R1, R2, R7 and Z each have the same meaning as defined before.
  • R1, R2, R7 and Z each have the same meaning as defined before.
  • adamantane-1,3,5-triol tri­caprylate which is a compound expressed by the above given general formura (II) in which R1, R2 and R3 are each a n-heptyl group and Z is a hydrogen atom, has properties shown in Table 1 below and is highly heat resistant and excellent in both of the low temperature characteristics and high temperature cha­racteristics as a synthetic lubricating oil with a high kine­matic viscosity even at high temperatures despite the low pour point as compared with adamantane diol dicaprylate and adamantane monool monocaprylate.
  • Table 1 is highly heat resistant and excellent in both of the low temperature characteristics and high temperature cha­racteristics as a synthetic lubricating oil with a high kine­matic viscosity even at high temperatures despite the low pour point as compared with adamantane diol dicaprylate and adamantane monool monocaprylate.
  • the higher carboxylic acid triester of adamantane triol according to the present invention is excellent in both of the low temperature characteristics and high temperature characteristics so that it is useful as a high-performance synthetic lubricat­ing oil.
  • the lubricating oil is formulated either with a single kind of the triesters or with two kinds or more thereof in combination. It is further optional that one kind or more of the higher carboxylic acid triesters of adamantane-1,3,5-triol are combined with one kind or more of higher carboxylic acid triesters of 7-hydroxyadamantane-1,3,5-triol derived from adamantane-1,3,5,7-tetraol.
  • the reaction mixture in the autoclave was heated up to a temperature of 250°C under agitation and kept at this tem­perature for 5 hours to effect the hydrolysis reaction. After the end of the reaction time, the autoclave was cooled to room temperature and the reaction mixture taken out of the auto­clave was admixed with 1.6 g (0.0402 mole) of sodium hydroxide to decompose the pyridinium salt.
  • reaction mixture was freed from pyridine and water by distillation to leave a residue which could be identified by the gas chromato­graphic analysis (FID-OV-101) to be a mixture composed of 41% by weight of adamantane-1,3,5-triol, referred to as 1,3,5-­Ad(OH)3, 36% by weight of dehydroadamantane diols, referred to as DHAd(OH)2, 10% by weight of monobromo adamantane diol, referred to as Ad(OH)2Br, and 9% by weight of others.
  • DHAd(OH)2Br 1,3,5-­Ad(OH)36% by weight of dehydroadamantane diols
  • Ad(OH)2Br monobromo adamantane diol
  • the residue was admixed with 200 ml of sulfuric acid of 5% by weight concentration and agitated for 30 minutes at 80°C followed by neutralization with sodium hydroxide and removal of the suspended matter by filtration.
  • the filtrate was sub­jected to evaporation of water to dryness on a rotary evapo­rator to give a crystalline mixture composed of Ad(OH)3, sodium bromide and sodium sulfate.
  • the thus obtained crystalline mixture was admixed with 50 ml of ethyl alcohol and agitated for 30 minutes followed by filtration to give an ethyl alcohol ex­tract as the filtrate.
  • the residue was further subjected to extraction with ethyl alcohol in the same manner.
  • the ethyl alcohol extracts were combined and subjected to evaporation of ethyl alcohol to dryness on a rotary evaporator to give 2.3 g of a light yellow crystalline product.
  • the reaction mixture was further agitated at 100°C for additional one hour followed by removal of most part of water and acetic acid by evaporation on a rotary evaporator. Thereafter, the residue after evaporation was dissolved by adding about 1 liter of deionized water to give an aqueous solution which was neutralized to have a pH of 7 by adding a small amount of sodium hydroxide solid. The thus neutralized solution was subjected to evaporation of water on a rotary evaporator until the whole volume thereof was reduced to about 1 liter.
  • the reaction mixture in the flask was agitated for additional two hours at 90°C and subjected to evaporation of most part of water and acetic acid therefrom on a rotary evaporator. Thereafter, the residue after evaporation was ad­mixed with about 1 liter of water and neutralized with sodium hydroxide to have a pH of 7 in the same manner as before.
  • caprylic chloride (reagent grade, a product by Tokyo Kasei Co.) taken in a four-necked flask of 1 liter capacity and heated at 90°C under a stream of nitrogen gas with agitation were added 80 g (0.43 mole) of the above obtained adamantane triol. Hydrogen chloride gas was evolved from the reaction mixture which was further agitated for 1 hour with the temperature increased to 140°C.
  • reaction mixture was admixed with 500 ml of hexane and an aqueous solution prepared by dissolving 200 g of sodium hydrogen carbonate in 2 liters of water and the mixture was agitated for 24 hours at room temperature.
  • the mixture was kept standing to be separated into two layers and subjected to phase separation to discard the aqueous alkaline solution.
  • the organic solution was washed twice with water and then dried over anhydrous sodium sulfate followed by removal of hexane by distillation.
  • the product was subjected to distil­lation under the conditions of a reduced pressure of 1 mmHg and a bottom temperature of 210°C to remove the acid chloride remaining in the mixture in a trace amount so that a liquid product in an amount of 240 g was obtained as the distillation residue.
  • the yield was 98% of the theoretical value.
  • FIGS 1, 2 and 3 of the accompanying drawing each show a diagram of 13C NMR spectrum, 1H NMR spectrum and infrared absorption spectrum, respectively, of the thus obtained liquid product.
  • a strong absorption band is noted at a wave number of 1725 cm ⁇ 1 in the infrared absorption spectrum, which is assignable to the stretching vibration of the carbonyl groups.
  • the results of the elementary analysis of this product were: C 72.2%; H 10.4%; and O 16.7%, as found (C 72.6%; H 10.3%; and O 17.1%, as calculated for C34H58O6).
  • Table 1 shown above summarizes several parameters for the primary evaluation of the thus obtained adamantane-1,3,5-­triol tricaprylate, as a lubricating oil, together with the corresponding properteis of adamantane-1,5-diol dicaprylate, and adamantane monool caprylate.
  • the compound has a high kinematic viscosity of 9.55 centi­stokes at 100°C despite the low pour point of -50°C or below.
  • a compound having a pour point of -50°C or below has a kinematic viscosity at 100°C of 4 to 5 centi­stokes, as is the case in trimethylol propane tricaprylate, from the general relationship between the pour point and the kinematic viscosity at 100°C in hindered ester compounds having excellent heat resistance.
  • the adamantane-1,3,5-triol tricaprylate according to the present invention has a kinematic viscosity at 100°C larger by about 5 to 6 centistokes than the above mentioned conventional compound. This property is very important for a synthetic lubricating oil.
  • a synthetic lubricating oil having a low pour point but high kinematic viscosity at elevated temperatures can be used in an ambience of very low temperature of, for example, -53°C or below, which is the pour point required for a jet engine oil, while an oil film having a sufficiently large thickness can be obtained on a surface lubricated with the lubricating oil even at high temperatures.
  • the compound is characterized by the very high thermal stability. As is understood from the temperature of the exo­thermic peak in the differential thermal analysis in an air stream, it is apparent that the adamantane-1,3,5-triol tri­caprylate according to the present invention has very high thermal stability in an oxidizing atmosphere as compared with adamantane diol dicaprylate and adamantane monool caprylate.
  • the higher carboxylic acid triester of adamantane triol ac­cording to the present invention which is a novel compound not described in any prior art literatures, has excellent thermal stability and, despite the low pour point, has a high kinematic viscosity at high temperatures so that it is useful as a high-performance lubricating oil which is required to be excellent in both of the low-temperature characteristics and high-temperature characteristics.
  • the synthetic lubricating oil of the present invention of which the principal ingredient is the higher carboxylic acid triester of adamantane triol, has excellent charac­teristics mentioned above so that it can be used quite satisfactorily, for example, as an engine oil, gear oil, hydraulic working fluid, grease, vacuum pump oil, bearing-­impregnating oil, gas turbine oil and the like.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Lubricants (AREA)
EP89118697A 1988-10-12 1989-10-07 Triesters d'acides carboxyliques supérieurs d'adamantetriol et huiles lubrifiantes les contenant Ceased EP0363866A3 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP25499788A JPH02104553A (ja) 1988-10-12 1988-10-12 アダマンタントリオールの高級カルボン酸トリエステル及びこれを含有して成る合成潤滑油
JP254997/88 1988-10-12
JP17253/89 1989-01-26
JP1017253A JP2678784B2 (ja) 1989-01-26 1989-01-26 アダマンタントリオール類の製造方法

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EP0363866A2 true EP0363866A2 (fr) 1990-04-18
EP0363866A3 EP0363866A3 (fr) 1990-06-20

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GB8629690D0 (en) * 1985-12-20 2013-10-16 Stauffer Chemical Co High temperature synthetic lubricant
US5397488A (en) * 1993-12-09 1995-03-14 Mobil Oil Corporation Oxidatively stable esters derived from diamondoids totally hydroxylated at the bridgeheads
US6133488A (en) * 1996-11-21 2000-10-17 Daicel Chemical Industries, Limited Processes for separating adamantanols
JP4938250B2 (ja) * 2005-04-28 2012-05-23 出光興産株式会社 動力伝達用潤滑剤
CN109536254B (zh) * 2018-11-27 2021-09-14 苏州金钼润成润滑科技有限公司 金钢烷氮钼润滑剂及其制备方法
RU2704978C1 (ru) * 2018-12-26 2019-11-01 федеральное государственное бюджетное образовательное учреждение высшего образования "Самарский государственный технический университет" Основа смазочного масла

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US3342880A (en) * 1963-03-14 1967-09-19 Du Pont Adamantane derivatives
US3398165A (en) * 1966-03-02 1968-08-20 Sun Oil Co Diesters containing adamantane nuclei
SU857101A1 (ru) * 1979-12-19 1981-08-23 Калининский Ордена Трудового Красного Знамени Политехнический Институт Способ получени 1,3-диоксиадамантана

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US4990691A (en) 1991-02-05
US4963292A (en) 1990-10-16

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